Melamine-formaldehyde laminating syrup



2.740.737. MELAMINEAFORMALDEHYDE LAMINATINGL SYRUP Curtis Elmer and ThomasAnas, Springfield,- and- Stuart HvRider, Longmeadow, Mass.-,-.assignors to Monsanto Chemical Company, St. Louis, Mo., a corporation of Delaware No Drawing. Application -July'fig1954; I

Serial No.-441=,6.l3

S Claims. Cl. 154-43; i

This invention relates to laminating resins; More particularly, the invention relates to laminating resinshaving increased flow at -.lower-' volatiles content;

In the preparation of laminates and especiall'wpapei'. laminateswmade from a plurality oflaminae, the. volatile or moisture content of the laminae before pressing is-a.

major problem. The volatiles,.usua1ly:- water but sometimesorganic solvents, must-r be removedfrom the final.

laminate and if they constitute too great-apercentagezofthe Weight of the impregnated paper, they cause poor adhesion, blow holes, poor. gloss, high moisture absorption, and other seriousdefects. However, ifithe volatiles are reduced before lamination toalevel at-which these1 prop. erties-areat their optimum level, the resinstdonot flow outevenly in the laminating process.-

One of the major advances in this field has been the:

introductionof laminating resinsprepared from melamine, toluene sulfonamide and formaldehyde. have: sufficient-flow near optimum volatiles. content to-v yielda good laminate agreater-part of the time. How-: ever, there is frequent failure to produce-goodslaminateswith these resins even under carefully controlled conditions;

One object-of this invention is to provide new laminating resins.

Another objectis to provide-laminating-,resins. having increased flow at optimum volatiles. content.

A further object is to" provide laminates atleast the topmost layer'ofwhich is impregnated with and bonded. to the remainder of the laminate witha modified melamine-toluene 'sulfonamide-formaldehyde resin.

These and other objects are attained by modifying melamine-toluene sulfonamideeformaldehyde resins- With from 0.0006 to ;006 mol of ammeline, ammelide, cy-- anuric acid or mixtures thereof per. molofmelamine:

. .The. following examples are givenin-illustration .and. are not intended aslimitations on the'scope of-.this= inven-- tion. Where parts are mentioned, they are:parts;-by.weight.

EXAMPLE I Disperse 126 parts .(one mol) of melamine-.202 parts (about 2.5 mols) of .formaline (3.7%, formaldehyde) and 0.5 part (about 0.004 mol) of ammeline in 60 parts of water and adjust the-pH ofthe dispersion to about 82 5 with sodium hydroxide. Heat the dispersion with constant agitation at reflux temperature and atmospheric pressure for about 30 minutes. Add to the reaction medium, 40 parts (about 0.25 mol) of p-toluene sulfonamide and reduce the pH of the medium to 7-8 with formic acid. Continue heating the reaction mixture at reflux temperature and atmospheric pressure until a cloud point of l020 C. is reached. Cool and filter.

The product of Example l is an aqueous solution of a co-condensation product of melamine, ammeline, ptolu'- ene sulfonamide and formaldehyde. The condensation product may be recovered from solution by conventional These resins:

2,740,737 Eatented. Apr... 3,.v 1856 but its: flow properties are particularly suitable; for pre paring laminates from paper,;wood, cloth; etc.

To prepare laminates, vthe'resinsare normally dissolvedx inwater. or. a mixture of water, and. an aliphatic. alcohol such asmethanol,-. ethanol, propanol, isopropanoL. the. various butanols etc. For best results, from. 2,0.-to. 301 parts of alcoholnare usedfor. every 100parts-ofwater: The resincontent of the solution. should. range. from: 40. to.60 byweight.

One method-of preparing. laminates-especially for test purposes. is as-follows EXAMPLE II I Impregnate, 4 mil rayon-rag paper with:;a.60% solids 5011mm of the. co.-con.densation. product .of. Eita'mple [lint a water-ethanol (100-20.);solventkbynippihggthe p apenin. the solution .and,.withdrawing; it .slowlyv therefrombvera scraper. bar or. through. metering. rolls. to; remove; excess. solution. Cut tli'ewet impregnatedpap'en into..a.p li1rality. of 1%: inch circular. pieces- Divide the circles. into; five.

' setsof twelve. each. Dry eaehsetfor, a.ditferentiperi 'o.df

drying methods such as spray drying, oven drying, etc. The

dried resin may be used as a soft-flow molding powder of timein-a'circulating ainovenat120C.

To laminate the-circlesandiestflow properties-Iofftlie. resin;.sup erimpose the twelvecircles ineaclisetintoa stack. Weigh the. stack.v Laminate the. st ack, .under..a. pres sure.ofl'1l)0.0'p.- s. i. at 15.0. C. for."3.minutes. C'oo'l' the. laminate,,.cut.. off. the flash, ii. e.,v theresin} whiclil ias. fiowedout beyondtlie.periphery;ofltlieIamiiiateandEWeigli the trimmed laminate. The flow. of ,the. resiniscalculated'. by dividing the.weightofi'the flash by. thetotalrwei glittof,

, the original compressed stack.

TableI setstforth the .resultsobtainedawith .the {reaction productof. Example Ilascoinparedgwith a .reactionproduct of; melamine, p toluen'ei sul'fonamide. and." formaldehyde. withoutthe addition offammeline. 1

A" is the co-condensate'ot'melamine; p-t'olneneisulfonamide; ammeline andformaldehyde. 4 B- isthe co-eondensate of melamine, p toluene sulfonamide and formaldehyde. Y

The data in Table Iv show that the inclusion'ofammelih'e in the co-condensation product of melamine; p-to l'u'ene sulfonamide and formaldehydefyields a product having; a greater flow. at high volatilescontent'andthat thedifferential in flow becomes greater as the volatiles are decreased.

EXAMRLEzIII'; Prepare a series off resins as -shown" in" Example Ibu't replacing the ammeline with ammelid'e ot cyanuric' acid? Make andtest laminates as 'shown' in Example. H5 The results obtained are set forth in Table II? Table II' Volatiles, Percent... Flow, Percent 2 to 5 mols, the toluene sulfonamide to from 0.1 to 1.0 mol and the ammeline, ammelide, cyanuric acid or mixtures thereof, to from 0.0006 to 0.006 mol, respectively.

The formaldehyde is most conveniently used in the form of formalin which is a 37% aqueous solution of formaldehyde. Pure formaldehyde or its polymers, parse formaldehyde and trioxymethylene, may be used.

The reaction should be carried out by reacting to gether the melamine, ammeline, ammelide, cyanuric acid or mixtures thereof and formaldehyde at a pH of from 8 to 10 until partial condensation has occurred and then adding the toluene-sulfonamide and adjusting the pH to from 7 to 8. The temperature of the reaction is preferably refiux temperature at atmospheric pressure but temperatures as much as 50 C. below r'eflux may be used if desired.

The reaction should be carried out in an aqueous medium using sufficient water to render the reaction medium fluid. An excess of water may be used and the excess removed at the end of the reaction.

For preparing laminates, the syrup obtained at the end of the reaction may be used directly but generally the viscosity is too high at the desired solids content if water is the only solvent. A more usable viscosity is obtained if the aqueous solution is modified by the inclusion of from 2 0 to parts of a lower aliphatic monohydric alcohol containing from '1 to 8 carbon atoms for every 100 parts by weight of water. The solids content of the laminating syrups should range from 40 to 60% by weight.

The amount of resin used in paper laminates will vary according to the properties desired. A deposit of -70% by weight of resin in and on the paper is sufiicient for most purposes. In preparing the laminates for the flow tests described above, a resin pickup of from 60 to 65% is required.

The resins of this invention can be cured to an insoluble infusible state by heat at temperatures between 120 and 160 C. preferably under substantial pressure. The physical and chemical properties of the cured resin are equivalent to melamine-toluene sulfonamide-formaldehyde resins unmodified by ammeline in all respects except the greatly increased flow.

Due to the light color of these resins, they are particularly valuable for use in preparing decorative laminates in which a decorative surface sheet is laminated to a solid or laminated core. Most frequently, the core consists of a laminate made from a plurality of paper plies bonded with a thermosetting resin such as, for example, a phenolic or alkyl resin. In some cases, the core is a solid block of wood and in others it is the so-called hardboard which comprises wood waste bonded with a thermosetting resin under high pressure. The decorative sheet may be of paper, or various textile materials such as cotton, glass, nylon, vinyl resin, etc. fabrics.

For example, a decorative laminate may be prepared as follows:

Impregnate eight sheets of kraft paper with a standard phenolic laminating varnish. Impregnate one sheet of bleached kraft paper having a design printed thereon with the syrup of Example I. Impregnate a second sheet of bleached kraft paper carrying no design with the syrup of Example I. Dry the impregnated sheets to remove excess volatiles. Superimpose the eight sheets one on another to form an initial assembly. Place the printed sheet on top of the initial assembly and the unprinted sheet on top of that. Laminate the assembly under 1000 p. s. i. pressure at C. for 30 minutes. The product is an attractive laminate, the topmost layer of which displays the decorative print unmarred by color due to the laminating resin and having superior gloss and abrasion resistance.

In decorative laminates of this type, the topmost layer is thin enough to be substantially transparent after laminating and serves mainly as extra protection for the printed surface.

What is claimed is:

1. A co-condensation product of one mol of melamine, from 2 to 5 mols of formaldehyde, from 0.1 to 1 mol of toluene sulfonamide and from 0.0006 to 0.006 mol of a material taken from the group consisting of ammeline, ammelide, cyanuric acid and mixtures thereof.

2. A product as in claim 1 wherein the material is ammeline.

3. A product as in claim 1 wherein the material is ammelide.

4. A product as in claim 1 wherein the material is cyanuric acid.

5. A product as in claim 1 wherein the material is a mixture of cyanuric acid and ammelide in which the ammelide constitutes about 20% by weight of the mixture.

6. A process of preparing a high flow melamine resin which comprises reacting one mol of melamine with from 2 to 5 mols of formaldehyde and from 0.001 to 0.006 mol of a compound taken from the group consisting of ammeline, ammelide, cyanuric acid and mixtures thereof at a pH of from 8 to 10 and at a temperature ranging from reflux temperature to 50 C. below reflux temperature at atmospheric pressure, adding to the reaction product from 0.01 to 1.0 mol of toluene sulfonamide, adjustthe pH to from 7 to 8 and continuing the reaction at from reflux temperature to 50 C. below reflux temperature at atmospheric pressure.

7. A laminate comprising a plurality of laminae impregnated and bonded with a co-condensation product of one mol of melamine, from 2 to 5 mols of formaldehyde, from 0.1 to 1.0 mol of toluene sulfonamide and from 0.001 to 0.006 mol of a compound taken from the group consisting of ammeline, ammelide, cyanuric acid and mixtures thereof, said co-condensation product having been cured to an insoluble infusible state under heat and pressure during the process of preparing the laminate.

8. A laminate comprising a plurality of laminae at least the topmost layers of which are impregnated and bonded with a co-condensation product of one mol of melamine, from 2 to 5 mols of formaldehyde and from 0.0006 to 0.006 mol of a material taken from the group consisting of ammeline, ammelide, cyanuric acid and mixtures thereof, said co-condensation product having been cured in situ in the laminate to an insoluble infusible state under heat and pressure.

References Cited in the file of this patent UNITED STATES PATENTS 2,614,091 Bauer Oct. 14, 1952 

1. A CO-CONDENSTION PRODUCT OF ONE MOL OF MELAMINE, FROM 2 TO 5 MOLS OF FORMALDEHYDE, FROM 0.1 TO 1 MOL OF TOLUENE SULFONAMIDE AND FROM 0.0006 TO 0.006 MOL OF A MATERIAL TAKEN FROM THE GROUP 0.0006 TO 0.006 MOL OF A AMMELIDE, CYANURIC ACID AND MIXTURES THEREOF. 